JPS62227918A - Heat-resistant resin composition - Google Patents
Heat-resistant resin compositionInfo
- Publication number
- JPS62227918A JPS62227918A JP7049386A JP7049386A JPS62227918A JP S62227918 A JPS62227918 A JP S62227918A JP 7049386 A JP7049386 A JP 7049386A JP 7049386 A JP7049386 A JP 7049386A JP S62227918 A JPS62227918 A JP S62227918A
- Authority
- JP
- Japan
- Prior art keywords
- polyamine
- heat
- bismaleimide
- resin composition
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title abstract description 9
- 229920006015 heat resistant resin Polymers 0.000 title abstract description 6
- 229920000768 polyamine Polymers 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- -1 Maleimide compound Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 15
- 229920003192 poly(bis maleimide) Polymers 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000004982 aromatic amines Chemical class 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- FTFULVSESZARHS-UHFFFAOYSA-N 1-[2-chloro-4-[[3-chloro-4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(N2C(C=CC2=O)=O)C(Cl)=CC=1CC(C=C1Cl)=CC=C1N1C(=O)C=CC1=O FTFULVSESZARHS-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- YKOLZVXSPGIIBJ-UHFFFAOYSA-N 2-Isopropylaniline Chemical compound CC(C)C1=CC=CC=C1N YKOLZVXSPGIIBJ-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000258957 Asteroidea Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DGVMNQYBHPSIJS-UHFFFAOYSA-N dimagnesium;2,2,6,6-tetraoxido-1,3,5,7-tetraoxa-2,4,6-trisilaspiro[3.3]heptane;hydrate Chemical compound O.[Mg+2].[Mg+2].O1[Si]([O-])([O-])O[Si]21O[Si]([O-])([O-])O2 DGVMNQYBHPSIJS-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- BAZXQZYWJSBDRG-UHFFFAOYSA-N pyrrole-2,5-dione;toluene Chemical compound CC1=CC=CC=C1.O=C1NC(=O)C=C1.O=C1NC(=O)C=C1 BAZXQZYWJSBDRG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高温下での機械的特性の低下が少なく、かつ熱
安定性にｔ艷れた耐熱性樹脂組成物に関するものである
。この樹脂組成物は、多ノ・）積層用４Ｍ脂、摺動材料
、封止材料、成形材料および接着材として有用である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant resin composition that exhibits little deterioration in mechanical properties at high temperatures and has excellent thermal stability. This resin composition is useful as a 4M resin for lamination, a sliding material, a sealing material, a molding material, and an adhesive.
近年、電気・電子分野、飢空磯・単筒等の輸送機器分野
等においては機器の高性能化、小型軽量化に伴い耐熱性
のより優れた材料が望まれている。BACKGROUND ART In recent years, materials with better heat resistance have been desired in the electrical/electronic field and in the field of transportation equipment such as starfish and single cylinders, as equipment becomes more efficient, smaller and lighter.
従来、該分野においてはエポキシ樹脂、マレイミド樹脂
およびポリイミド樹脂等が用いられている。Conventionally, epoxy resins, maleimide resins, polyimide resins, etc. have been used in this field.
しかし、エポキシ樹脂は機械特性、７ｆＬ気特性に優れ
ているが耐熱性が必ずしも充分ではない。また、ポリイ
ミド樹脂は優れた耐熱性を有しているが、不溶不融であ
るため成形が田畑である。However, although epoxy resin has excellent mechanical properties and 7fL properties, its heat resistance is not necessarily sufficient. Furthermore, although polyimide resin has excellent heat resistance, it is difficult to mold it because it is insoluble and infusible.
成形加工性をカロ良したポリイミドとして付加型のビス
マレイミド樹力旨が公知である。しかしながら、付加型
のビスマレイミド但（脂を単に熱富合して得られる硬化
便脂はきわめて脆く、冷却、加熱等の熱衝撃により容易
にクラックを生じやすく、実用に耐え得るものではない
。かかる欠点を改良し、ビスマレイミドの耐熱性に優れ
た特性を生かし、しかも実用的に十分耐え得る樹脂とし
て、Ｎ、Ｎ’−４，４’−ジフェニルメタンビスマレイ
ミドと４．４′−ジアミノジフェニルメタンのプレポリ
マーであるポリアミノビスマレイミド樹脂が実用化され
た。しかし、この樹脂の特性を最大限発揮させるために
は、高温で長時間加熱することが必要であり、経済的に
不利である。そこで、このポリアミノビスマレイミド樹
脂にエポキシ樹脂を混会し、砕化性の改良が試みられて
いる（特公昭４７−４２１６０号公ｍ）ｏＬかし、この
配合で硬化させた硬化物は、高温での長時間の露出に対
しての安定性に劣り、ビスマレイミド本来の熱安定性が
発揮されないという問題を有している。Addition-type bismaleimide is known as a polyimide with good moldability and caloricity. However, the hardened stool fat obtained by simply heat-enriching addition-type bismaleimide (fat) is extremely brittle and easily cracks due to thermal shocks such as cooling and heating, making it unsuitable for practical use. A prepolymer of N,N'-4,4'-diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane was developed as a resin that takes advantage of bismaleimide's excellent heat resistance and has sufficient durability for practical use. Polyamino bismaleimide resin, which is a An attempt has been made to improve the crushability by mixing epoxy resin with bismaleimide resin (Japanese Patent Publication No. 47-42160). Bismaleimide has a problem in that it has poor stability against exposure and does not exhibit the inherent thermal stability of bismaleimide.
不発明は、これら樹脂の成形性、硬化性および熱安定性
を改良した耐熱性樹脂組成物を提供するためになされた
ものである。The invention was made in order to provide a heat-resistant resin composition that has improved moldability, curability, and thermal stability of these resins.
〔問題点を解決するための手段〕
本を明は、
回収分：一分子中に少なくとも２個のマレイミド基全方
するポリマレイミド化合物
ＣＢ）成分：一分子中に少なくとも２個のエポキシ基を
有するエポキシ化合物
（Ｃ）成分二下記一般式（１）で示されるポリアミン〔
式中、Ｘは水素原子、ハロゲン原子または炭素数１〜４
のアルキル基もしくはアルコキシ基である〕
上記（４）、（Ｂ）および（Ｃ）成分が配合されている
ことを特徴とする耐熱性樹脂組成物を提供するものであ
る〇
（ポリマレイミド化合物）
０υ成分の一分子中に少なくとも２個のマレイミドｆ：
、を有するポリマレイミド化合物としては、たとえば次
のものが昂げられる。[Means for solving the problem] This book is based on the following: Recovered portion: Polymaleimide compound having at least two maleimide groups in one molecule CB) Component: At least two epoxy groups in one molecule Epoxy compound (C) component 2 Polyamine represented by the following general formula (1) [
In the formula, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to 4
〇 (Polymaleimide compound) 〇 (Polymaleimide compound) 0υ At least two maleimides f in one molecule of the component:
Examples of the polymaleimide compound having , include the following.
（１） Ｎ、Ｎ’−エチレンビスマレイミド、Ｎ、Ｎ’
−ヘキサメチレンピスマレイミ）”、Ｎ、Ｎ’ −ｍ
−−ｙエニレンヒスマレイミ）’、Ｎ、Ｎ’ −ｐ−フ
ェニンンピスマレイミ）”、ＮＩＮ’−４，４’−ジフ
ェニルメタンビスマレイミド、Ｎ、Ｎ’−４，、ｉ’−
ジフェニルエーテルビスマレイミト、Ｎ、Ｎ′−メチレ
ンビス（３−クロロ−ｐ−フェニレン］ビスマレイミド
、Ｎ、Ｎ’−４，，１’−ジフェニルスルフォンビスマ
レ’ｆ ミド％ ＮＩＮ’ −４，４′−ジシクロヘキ
シルメタンビスマレイミド、Ｎ＋Ｎ’ ａ、α／
４，４／−ジメチレンシクロヘキサンピスマＬ／イミ）
’、ＮＩＮ’−ｍ−キシリレンビスマレイミド、Ｎ、Ｎ
’ ４．４’−ジフェニルシクロヘキサンビスマレイ
ミド、Ｎ、Ｎ’−４，４’−ジフェニル−１，１−プロ
パンビスマレイミ）”、ＮＩＮ’−４，４’−トＵ −
ｙユニルー１．１．１−エタンビスマレイミド、Ｎ、Ｎ
’−４，４’−トＩＪフェニルメタンビスマレイミド、
Ｎ、Ｎ’−３，５−トリアゾール−１，２，４−ビスマ
レイミド等のビスマレイミド。(1) N,N'-ethylene bismaleimide, N,N'
-hexamethylene pismaleimi)", N, N' -m
--yenylenehismaleimide)', N,N'-p-phenylenepismaleimide)',NIN'-4,4'-diphenylmethane bismaleimide, N,N'-4,,i'-
Diphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, N,N'-4,,1'-diphenylsulfonebismale'f Mid% NIN'-4,4'- Dicyclohexylmethane bismaleimide, N+N' a, α/
4,4/-dimethylenecyclohexane pisma L/imi)
', NIN'-m-xylylene bismaleimide, N, N
'4,4'-diphenylcyclohexane bismaleimide, N,N'-4,4'-diphenyl-1,1-propane bismaleimide)', NIN'-4,4'-tU-
y Uniru 1.1.1-ethane bismaleimide, N, N
'-4,4'-toIJ phenylmethane bismaleimide,
Bismaleimides such as N,N'-3,5-triazole-1,2,4-bismaleimide.
（ＩＩ）下記一般式で示されるポＩＪ（Ｎ−フェニルメ
チレン）マレイミド
〔式中、ｎはＯ〜４の数である。〕
（ｉｉｉ）下記一般式で示されるポリマレイミド（ｔ￥
ｊ開昭５９−１２９３１号公報参照）
〔式中、Ｘは水素原子、ノ・ロゲン原子または炭素数１
〜４のアルキル基もしくはアルコキシ基である〕
（１■）ホルムアルデヒド５〜９５重量係と芳香族ジア
ルデヒド９５〜５重量％の混合物よりなるアルデヒド類
１モルに対し、
一般式、
〔式中、Ｘは水素原子、ハロゲン原子または炭素数１〜
４のアルキル基もしくはアルコキシ基である〕
で示される芳香族アミンを２〜６０モルの割合で反応さ
せてポリアミンを得、次いで該ポリアミンに無水マレイ
ン酸を付加反応させてポリアミド酸を得た後、該ポリア
ミド酸を脱水環化して得られる、一般式
で示されるポリマレイミドと一般式
で示されるポリマレイミドを含有する混合物（特開昭６
０−２６０３２号公報番照）。(II) PolyJ(N-phenylmethylene)maleimide represented by the following general formula [wherein n is a number of O to 4]. ] (iii) Polymaleimide (t￥
(See Japanese Patent Publication No. 59-12931) [In the formula, X is a hydrogen atom, a hydrogen atom, or a carbon number 1
~4 alkyl group or alkoxy group] (1■) For 1 mole of aldehydes consisting of a mixture of 5 to 95% by weight of formaldehyde and 95 to 5% by weight of aromatic dialdehyde, the general formula, [wherein X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 is an alkyl group or an alkoxy group] to obtain a polyamine by reacting an aromatic amine represented by 2 to 60 moles, and then adding maleic anhydride to the polyamine to obtain a polyamic acid, A mixture containing a polymaleimide represented by the general formula and a polymaleimide represented by the general formula obtained by cyclodehydration of the polyamic acid (JP-A No. 6
0-26032).
〔式中、Ｘは水素原子、ハロゲン原子または炭素数１〜
４のアルキル基もしくはアルコキシ基であり、ｍは０か
ら４の整数である〕。[In the formula, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 alkyl group or alkoxy group, m is an integer from 0 to 4].
（エポキシ化合物）
（Ｂ）成分の一分子中に少なくとも２個のエポキシ基を
有するエポキシ化合物としては、たとえば次のものが挙
げられる。(Epoxy Compound) Examples of the epoxy compound having at least two epoxy groups in one molecule of component (B) include the following.
（１） ビスフェノールＡのジグリシジルエーテル：
その商品としては油化シェルエポキシ株式会社のエピコ
ート８２７、同８２８、同８３４、同８６４、同１００
１．同１００４．１ｆｆＪ １００７、同１０３１、チ
バ社のアラルダイトＧＹ２５０、同６０９９、ユニオン
カーバイド社のＥＲＬ２７７４、ダウケミカル社のＤＥ
Ｒ３３２、同３３１゜同６６１、（以上いずれも商品名
）等。(1) Diglycidyl ether of bisphenol A:
The products include Epicoat 827, 828, 834, 864, and 100 from Yuka Shell Epoxy Co., Ltd.
1. 1004.1ffJ 1007, 1031, Ciba Araldite GY250, 6099, Union Carbide ERL2774, Dow Chemical DE
R332, R331° R661, (all of the above are product names), etc.
（１１） エポキシフェノールノボラック：その商品
としては油化シェルエポキシ株式会社のエピコート１５
２、同１５４、ダウケミカル社のＤＥＮ４３８、同４４
８、チバ社のアラルダイトＥＰＮ１１３８、同１１３９
（以上いずれも商品名）等。(11) Epoxyphenol novolak: The product is Epicoat 15 from Yuka Shell Epoxy Co., Ltd.
2, 154, DOW Chemical Company DEN438, 44
8. Ciba's Araldite EPN1138, EPN1139
(All of the above are product names) etc.
（ＩｉＤ エポキシクレゾールノボラック；その商品
としてはチバ社のアラルダイトｇｃＮ１２３５、同１２
７３、同１２８０（以上いずれもｌ？６品名）等０
その他、ビスフェノールＦのジグリシジルエーテル、フ
タル酸又はヘキサヒドルフタル酸とエピクロルヒドリン
からイ与られるエポキシｍｇｈ、ノくラハイドロオキ７
安息香酸とエピクロルヒドリンより得られるエポキシ樹
脂、トルイジンやアニリン等の芳香族アミンとエピクロ
ルヒドリンより得られるエポキシ樹脂、ビニルシクロヘ
キセンジオキシド、ｌ、４−ブタンジオールジグリシジ
ルエーテル、１．６−ヘキサンシオールジグリシジルエ
ーテル等があげられる。(IiD epoxy cresol novolak; its products include Ciba's Araldite gcN1235 and 12
73, 1280 (all of the above are 1?6 product names), etc. 0 In addition, diglycidyl ether of bisphenol F, epoxy mgh obtained from phthalic acid or hexahydrophthalic acid and epichlorohydrin, Nokurahydroki 7
Epoxy resin obtained from benzoic acid and epichlorohydrin, epoxy resin obtained from aromatic amine such as toluidine or aniline and epichlorohydrin, vinylcyclohexene dioxide, l,4-butanediol diglycidyl ether, 1,6-hexanesiol diglycidyl ether etc. can be mentioned.
（ポリアミン〕
（Ｃ）成分の四官能ポリアミンは、芳香族ジアルデヒド
１モルに対し、
一般式
〔式中、Ｘは水素原子、）＼ロゲン原子または炭素数１
〜４のアルキル基もしくはアルコキシ基である〕
で示される芳香族アミンを２〜６０モルの割合で反応さ
せて得られる前記一般式（１）で示されるポリアミンを
主成分とするものである（特開昭５８−２２５０４３９
公報参照）０
原料の芳香族ジアルデヒドとしては、下記一般式
で示される化せ物、具体的には１．２−ベンゼンジアル
デヒド、ｌ、３−ベンゼンジアルデヒド、１．４−ベン
ゼンジアルデヒドか好ましく、これニノ・ロゲン基、ア
ルキル基等の置換基を有するものであってもよい。(Polyamine) The tetrafunctional polyamine of the component (C) has the general formula [wherein, X is a hydrogen atom]\rogen atom or carbon number 1
~4 alkyl group or alkoxy group] The main component is a polyamine represented by the above general formula (1) obtained by reacting an aromatic amine represented by 2 to 60 moles (particularly Kaisho 58-2250439
(Refer to the publication) 0 The aromatic dialdehyde used as a raw material is a compound represented by the following general formula, specifically 1,2-benzenedialdehyde, 1,3-benzenedialdehyde, 1,4-benzenedialdehyde. It is preferable that it has a substituent such as a nino-logen group or an alkyl group.
また、芳香族アミンとしては、アニリン、０−トル・１
ジン、ｍ−トルイジン、ｐ−トルイジン、０−エチルア
ニリン、Ｏ−イソプロピルアニリン、ｐ−ブチルアニリ
ン、０−アニンジン、Ｉｎ−７ニシシン、ｐ−アニシジ
ン、０−フェネチジン、クロルアニリン類、ブロムアニ
リン類等が挙げられる。In addition, aromatic amines include aniline, 0-tolu・1
gin, m-toluidine, p-toluidine, 0-ethylaniline, O-isopropylaniline, p-butylaniline, 0-anidine, In-7 Nishicine, p-anisidine, 0-phenetidine, chloraniline, bromoaniline, etc. can be mentioned.
芳香族ジアルデヒドと芳香族アミンとの反応は、塩酸、
硫酸等の鉱酸類、蓚酸、パラトルエンスルフォン酸等の
有機酸類、その他の有機酸塩類等の酸性触媒の存在下に
、芳香族ジアルデヒド、１モルに対して、芳香族アミン
２〜６０モル、好ましくは５〜５０モルの割合で４０
〜１５０℃の温度で、１〜１０時間縮合反応を行う。The reaction between aromatic dialdehyde and aromatic amine is carried out using hydrochloric acid,
In the presence of an acidic catalyst such as mineral acids such as sulfuric acid, organic acids such as oxalic acid and para-toluenesulfonic acid, and other organic acid salts, 2 to 60 moles of aromatic amine per mole of aromatic dialdehyde, Preferably 40 to 50 moles
The condensation reaction is carried out at a temperature of ~150<0>C for 1 to 10 hours.
反応終了後、反応混合物を水酸化ナトリウムで代表され
るアルカリを用いて中和し、水洗を行った後に過剰の芳
香族アミンを減圧除去することによりポリアミンを得る
ことができる。After the reaction is completed, the reaction mixture is neutralized using an alkali such as sodium hydroxide, washed with water, and then excess aromatic amine is removed under reduced pressure to obtain a polyamine.
得られるポリアミンは常温で固体であり、前記一般式Ｃ
Ｉ）で示される構造を有するものが６０７１ｆ常係以上
である。The obtained polyamine is solid at room temperature and has the general formula C
Those having the structure shown in I) are 6071f or higher.
この式（Ｉ）で示されるポリアミンの他に、この式（１
）で示されるポリアミンに更に芳香族アルデヒドが縮合
反応し、そこに更に芳香族アミンが反応し７’ＣＮＨ□
基を７以上有する次式ゆで示されるポリアミンが４０３
１ｉ４Ｊ％以下の割合で（４）られる０Ｎ）１２
ＮＨ２〔式中のＸは（１１式と同じで
あり、Ｙｌ、Ｙ２、Ｙ３、Ｙ４ はＨまたは
λ
であり、Ｙ１′、Ｙ２′、Ｙ３′はＨまたはであり、ｙ
、 ／／、Ｙ２″、Ｙ３″はＨまたはである〕０
これらＮＨ２基を７個以上有するポリアミンの存在はゲ
ルパーミェーションクロマトグラフにより確認された。In addition to the polyamine represented by this formula (I), this formula (1)
), an aromatic aldehyde further undergoes a condensation reaction, and an aromatic amine further reacts therewith to form 7'CNH□
A polyamine having 7 or more groups represented by the following formula is 403
1i4J% or less (4)0N)12
NH2
, //, Y2'', Y3'' are H or ]0 The presence of these polyamines having 7 or more NH2 groups was confirmed by gel permeation chromatography.
会
（４）、（Ｂ）およびＣ）成分の配勿量は、囚成分１０
０重量部に対して、（Ｂ）成分は、１０〜９００重量部
、（Ｑ成分は５〜９ｏＯ！ｆｆｉ部の割合で使用される
０（Ｃ）成分のポリアミンは、ポリマレイミドおよびエ
ポキシ化合物の硬化剤として作用し、ポリアミンの配合
量が５Ｍｆｉｔ部未満であると硬化物がもろくなる。ま
た、９００ｉ量部を越えると硬化物の耐熱性が劣る。The amount of ingredients (4), (B) and C) is 10
Component (B) is used at a ratio of 10 to 900 parts by weight, and component (Q) is used at a ratio of 5 to 90!ffi parts to 0 parts by weight. It acts as a curing agent, and if the amount of polyamine is less than 5 Mfit parts, the cured product will become brittle.If it exceeds 900 I parts, the cured product will have poor heat resistance.
本発明の耐熱性組成物には、必要に応じて次の成分を添
加することができる。The following components can be added to the heat-resistant composition of the present invention as necessary.
（１）粉末状の補強剤や充てん剤、たとえば酸化アルミ
ニウム、酸化マグネシウムなどの金属酸化物、水酸化ア
ルミニウムなどの金属水酸化物、炭酸カルシウム、炭酸
マグネシウムなど金属炭酸塩、ケインク土粉、塩基性ケ
イ酸マグネシウム、焼成りレイ、微粉末シリカ、溶融シ
リカ、結晶シリカ、カーボンブラック、カオリン、微粉
末マイカ、石英粉末、水酸化アルミニウムなどの金属水
酸化物、グラファイト、アスベスト、二硫化モリブデン
、三酸化アンチモンなど。さらに繊維質の補強材や光て
ん剤、たとえばガラス繊維、ロックウール、セラミック
繊維アスベスト、およびカーボンファイバーなどの無ａ
［ｔＲ維や紙、パルプ、木粉、リンターならびにポリア
ミドＦｌｕなどの合成繊維などである。これらの粉末も
しくは繊維質の補強材や充てん剤の使用量は用途により
異なるが積層材料や成形材料としては囚と（Ｂ）成分の
和の樹脂組放物１００ ：ｉＭ部に対してｓｏｏｗ量部
まで使用できる。(1) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, clay powder, basic Magnesium silicate, fired clay, finely powdered silica, fused silica, crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum disulfide, trioxide such as antimony. In addition, fibrous reinforcements and photoresists, such as glass fibers, rock wool, ceramic fiber asbestos, and carbon fibers,
[These include tR fibers, paper, pulp, wood flour, linters, and synthetic fibers such as polyamide Flu. The amount of these powder or fibrous reinforcing materials and fillers to be used varies depending on the application, but for laminated materials and molding materials, the amount of resin composition of the sum of the powder and (B) component is 100: soow parts to iM parts. Can be used up to
（２）着色剤、顔料、難燃剤たとえば二酸化チタン、黄
鉛カーボンブラック、鉄黒、モリブデン赤、紺宵、群背
、カドミウム黄、カドミウム赤、赤リン等の無機リン、
トリフェニルフォスフエイト等の有機リンなどである。(2) Colorants, pigments, flame retardants such as titanium dioxide, yellow lead carbon black, iron black, molybdenum red, Konyoi, Gunsei, cadmium yellow, cadmium red, inorganic phosphorus such as red phosphorus,
These include organic phosphorus such as triphenyl phosphate.
（３）さらに、最終的な塗膜、接着層、樹脂成形品など
における樹脂の性質を改碧する目的で種々の合成樹脂を
配合することができる。たとえばフェノール樹脂、アル
キド樹脂、メラミン樹脂、フッ素樹脂、塩化ビニル樹脂
、アクリル樹脂、シリコーン樹脂、ポリエステル樹脂等
のｌ独またＶｉＺａ以上の組み合せを挙げることができ
る。これらの樹脂の使用量は本発明の樹脂組放物本来の
性質を損わない範囲量、すなわち、全樹脂量の５０重量
係未満が好ましい。(3) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. Examples include combinations of phenol resins, alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, polyester resins, and more than ViZa. The amount of these resins used is preferably within a range that does not impair the inherent properties of the resin composition of the present invention, that is, less than 50% by weight of the total resin amount.
（４）成分、（７３）成分および各オ」添加剤の配合手
段としては、加熱浴融混せ、ロール、ニーダ−等を用い
ての混練、適当な有機溶剤を用いての混合及び乾式混合
等があげられる。The means for blending component (4), component (73), and each additive include heating bath melting, kneading using a roll, kneader, etc., mixing using an appropriate organic solvent, and dry mixing. etc. can be mentioned.
本発明の耐熱性樹脂組成物は、従来のポリアミノビスマ
レイミド系樹脂と比較して耐熱性に誕れる硬化物を与え
る。The heat-resistant resin composition of the present invention provides a cured product that is more heat resistant than conventional polyamino bismaleimide resins.
以下、笑験例により不発明を更に詳細に説明する０
ポリアミンの製造例
例１
温Ｕ計、冷却器、攪拌装置を備えた三ロフラスコ内に１
．３−ベンゼンジアルデヒド３０ ｆ （０，２２４モ
ル）、アニリン１６６．６ ？ （１，７９モル）、−
塩酸６．８２を仕込み、水の速流化（温度１０７℃）で
５時間反応させた。Hereinafter, the non-invention will be explained in more detail using experimental examples.0 Example of manufacturing polyamine Example 1 In a three-hole flask equipped with a thermometer, a cooler, and a stirring device,
．． 3-benzenedialdehyde 30 f (0,224 mol), aniline 166.6 ? (1,79 mol), -
6.82 g of hydrochloric acid was charged, and the reaction was carried out for 5 hours with a rapid flow of water (temperature: 107° C.).
反応終了後、２０チの水酸化ナトリウム水溶液２０９５
１；加え、５分間債拌を続は中和反応を行った。次に、
メチルイソブチルケトン
え、析出物を溶解した後、純水３００２で計３ＬｏＩ水
況を行い、副成した塩化ナトリウム及び過剰の水酸化ナ
トリウムを除去した。After the reaction is complete, add 2095 liters of sodium hydroxide aqueous solution.
1; Added and stirred for 5 minutes, followed by neutralization reaction. next,
After dissolving the precipitate with methyl isobutyl ketone, a total of 3 LoI water conditions were performed using pure water 3002 to remove by-produced sodium chloride and excess sodium hydroxide.
次いで、溶解液を減圧下（１００〜１ｗＨｆ／８０〜１
８０℃ンテメチルイソブチルケトン及び未反応のアニＩ
Ｊンを児全に除去し、残留物を１８０℃で流し出し、冷
却して橙色透明な次式で示されるポリアミンを７７％有
するポリアミンの混合物１０１．Ｉ Ｐを得た。Next, the solution was heated under reduced pressure (100-1 wHf/80-1
80°C, temethyl isobutyl ketone and unreacted amine I
The residue was poured off at 180° C. and cooled to give an orange transparent mixture of polyamines having 77% of the following formula 101. I got IP.
このポリアミンの軟化点（毛細管法）は１１５〜１２１
℃、中和当ｉＬは１１８であった０例２
１．４−ベンセンジアルデヒド３０ ｒ （０，２２４
モル）、０−トルイジン９５．９ ？ （０，８９５モ
ル）およびアニリン８３．３９ （０，８９５モル）を
原料として用いる他は実施例１と同様にして赤色透明な
固体のポリアミンを１１１．９ ？得た。The softening point (capillary method) of this polyamine is 115-121
Example 2 1,4-benzenedialdehyde 30 r (0,224
mole), 0-toluidine 95.9 ? A red transparent solid polyamine was prepared in the same manner as in Example 1 except that aniline (0,895 mol) and aniline 83.39 (0,895 mol) were used as raw materials. Obtained.
このポリアミンの軟化点は１２２〜１２８℃であり、中
和当」は１２６であった。The softening point of this polyamine was 122 to 128°C, and the neutralization value was 126.
実施例Ｉ
Ｎ、Ｎ’ −４，４’ −ジフェニルメタンビスマレイ
ミド５０ 重ｉｎ部、ビスフェノールＡのジグリシジル
エーテル”エピコート８２８″（油化シェルエポキシ類
）５０宙を部、および製造例１で得たポリアミン２５．
５電量部を温度１３０℃で湿合し、脱泡後、金属の型内
に流し込み、１８０℃で３時間、次いで２３０℃で５時
間硬化を行い、縦１２７闘、４Ａ１２．７ ｗｓ、厚さ
６．４ ｍの硬化物を得た。Example I 50 parts of N,N'-4,4'-diphenylmethane bismaleimide, 50 parts of diglycidyl ether of bisphenol A "Epicote 828" (oiled shell epoxies), and 50 parts of N,N'-4,4'-diphenylmethane bismaleimide obtained in Production Example 1 Polyamine 25.
5 coulometric parts were moistened at a temperature of 130°C, degassed, poured into a metal mold, and cured at 180°C for 3 hours and then at 230°C for 5 hours. A cured product of 6.4 m was obtained.
この硬化物の物性値を表１に示す。Table 1 shows the physical properties of this cured product.
実施例２〜９、比紋例１
表１に示すマレイミド化合物、エポキシ化会物およびポ
リアミンを用いる他は実施例１と同様にして硬化物を得
た。Examples 2 to 9, Ratio Example 1 Cured products were obtained in the same manner as in Example 1, except that the maleimide compound, epoxidized compound, and polyamine shown in Table 1 were used.
結果を衣１に示す。The results are shown in Figure 1.
実施例１０
タレゾールノボラックエポキシ樹脂“ＥＯＣＮ−１０３
”（日本化薬製）５０東量部、Ｎ、Ｎ’−４゜ｉｔ’−
シ：ｙエニルメタンビスマレイミド５０可ｉＭＢ、例１
で得られ次ポリアミン２３重情部および溶融シリカ２０
０重量部を１００〜１２０℃の加熱ロールを用いて１０
分間混練した。Example 10 Talesol novolak epoxy resin “EOCN-103”
"(Nippon Kayaku) 50 parts, N, N'-4゜it'-
C:yenylmethane bismaleimide 50 iMB, Example 1
The following polyamine 23 polyester and fused silica 20
10 parts by weight using a heating roll at 100-120°C
Kneaded for a minute.
この混合物を粉砕機で粉砕して粒状化し、粒状物を加熱
プレスを用いて１８０℃１０分間、圧力５０ ｋｇ ／
ｃＪの条件で圧縮成形を行い、？ ｌ ２７１１１１
１横１２．７ｍｍ、厚さ６．４閣の成形物を得た。This mixture was pulverized using a pulverizer to form granules, and the granules were heated at 180°C for 10 minutes using a heating press at a pressure of 50 kg/kg.
Perform compression molding under cJ conditions, ? l 271111
A molded product with a width of 12.7 mm and a thickness of 6.4 mm was obtained.
この成形物を更ＶＣ２３０℃のオープンにて１０時間後
硬化させ、表２に示す物性の硬化物を得た。This molded product was post-cured for 10 hours in an open setting at VC 230°C to obtain a cured product having the physical properties shown in Table 2.
実施例１１
ポリアミンとして例２で得たポリアミノ全２４Ｎ社部用
いる他は実施例１０と同様にして表２に示す１１：ｒ！
化物を得た。Example 11 11:r! shown in Table 2 was carried out in the same manner as in Example 10 except that the polyamino 24N obtained in Example 2 was used as the polyamine.
I got a monster.
比較例２
ポリアミンとして４．４′−ジアミノジフェニルメタン
２２軍ｔｈｔ部用いる他は実施例１０と同様にして表２
に示す硬化物を得た０
表２Comparative Example 2 Table 2 was prepared in the same manner as in Example 10 except that 22 parts of 4,4'-diaminodiphenylmethane was used as the polyamine.
A cured product shown in Table 2 was obtained.
Claims (1)
を有するマレイミド化合物 （Ｂ）成分：一分子中に少なくとも２個のエポキシ基を
有するエポキシ化合物 （Ｃ）成分：下記一般式で示されるポリアミン▲数式、
化学式、表等があります▼ 〔式中、Ｘは水素原子、ハロゲン原子または炭素数１〜
４のアルキル基もしくはアルコキシ基である〕上記（Ａ
）、（Ｂ）、および（Ｃ）成分が配合されていることを
特徴とする耐熱性樹脂組成物。[Claims] Component (A): Maleimide compound having at least two maleimide groups in one molecule (B) Component: Epoxy compound having at least two epoxy groups in one molecule (C) Component: The following Polyamine represented by the general formula ▲ Formula,
There are chemical formulas, tables, etc.▼ [In the formula, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 is an alkyl group or an alkoxy group] above (A
), (B), and (C) components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7049386A JPS62227918A (en) | 1986-03-28 | 1986-03-28 | Heat-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7049386A JPS62227918A (en) | 1986-03-28 | 1986-03-28 | Heat-resistant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62227918A true JPS62227918A (en) | 1987-10-06 |
Family
ID=13433100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7049386A Pending JPS62227918A (en) | 1986-03-28 | 1986-03-28 | Heat-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62227918A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53134099A (en) * | 1977-04-28 | 1978-11-22 | Toshiba Corp | Heat-resistant resin composition |
| JPS58225043A (en) * | 1982-06-22 | 1983-12-27 | Mitsubishi Petrochem Co Ltd | Preparation of polyamine |
-
1986
- 1986-03-28 JP JP7049386A patent/JPS62227918A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53134099A (en) * | 1977-04-28 | 1978-11-22 | Toshiba Corp | Heat-resistant resin composition |
| JPS58225043A (en) * | 1982-06-22 | 1983-12-27 | Mitsubishi Petrochem Co Ltd | Preparation of polyamine |
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